Water-insoluble azo-dyestuffs and fiber dyed therewith



Patented Nov. 28, 1933 UNITED STATES PATENT OFFICE -WATER- INSOL UBLE AZO-DYESTUFFS FIBER DYED THEREWITH Arthur Zitscher, Offenbach-on-the Main, Germany, assignor to General AnilineWork's, Inc'., New York, N. Y., a corporation of Delaware No Drawing.

Application January 31, 1933,

' Serial No. 654,553, and in' GermanyFebruary 9,

8 Claims. (01. 2604s) The present invention relates to new waterinsoluble azo-dyestuffs and to fiberdyed therewith, more particularly it relates to compounds of the following general formula:

wherein R represents a radical of the benzene, naphthalene, diphenyl or anthraquinone series and Y stands for hydrogen, halogen or an alkoxy group. r

I have found that valuable, water-insoluble azodyestuffs are obtained by coupling adiazo compound with a 2-(3-hydroxynaphthyl-2)-4-hydroxy-G.7-benzo-pseudoaziminobenzene of r the following formula:

which may also be substituted in the benzene nuclei which do not contain'the hydroxy groups, either in substance, on the fiber or on any of the usual substrata adapted for the production of lakes, only such components being used which do not contain any group lending solubility, such as the sulfonic acid or carboxylic acid group.

The new dyestuffs may be used for the prepara-,

the yarn is then rinsed and soaped.

icals, with a '2-amino-3-hydroxynaphthalene, the hydrogen atom of the hydroxy group of which being likewise replaced by a suitable radical, eonreacting the ortho aminoazo dyestufi, thus formed, to the pseudoazimine according to known 7 methods and splitting; ofl the radicals linked to the hydroxy groups. They have,- in. contradis.- tinction to beta-naphthol, a certain aifinity for the fiber which allows to produce the dyestufis on the fiber without an intermediate drying of the grounded goods; The dyeings, thus "obtained, 2

possess a better *fastne'ss to soaping thanthose prepared by means ofcomparable combinations from beta-naphthol.

The following examples serve to illustrate. the

invention, but they are not intended to limit it thereto-the parts being by weight, unless other wi'se stated? Y l (1) Well boiled and dried cotton, yarn impregnated with a solution which contains tper liter 19 6.7-benzo-pseudoazimin obenzene, 20, cc. of caustic soda solution'of 34;B. and 20 cc. of Turkey red oil, thereupon, the yarn is developed in ajdia'zosolution which contains per liter. the diazoecompound from"1.62 grams'jof 2.5-dich1orani1ine and has been neutralied by means of sodium acetate;

There is obtained an orange dyeing. The dyestufi corresponds to the following formula: i

(2) 13.8 partsof l-amino-Z-nitrobenzene are diazctized in known manner. 'The diam-solution is combined with a solution prepared from 17 parts of 2- (3 -hydroXynaphtl1yl-"2 -4-hydroxy- 1631-henzmpseudoaziminobenzene in dilute caustic soda solution to which there has been added the quantity of sodium acetate necessary for binding the excess of mineral acid and 5 parts of Turkey red oil. The dyestufi separated is filtered by suction and washed well; it corresponds to the following formula:

lTTOe N N 03 N It may be used for the preparation of pigments, advantageously in the form of a paste;

mixed with substrata, a yellowish-red lake is obtained.

The following table indicates a number of other combinations obtainable according to the present process but it does not comprise all possibilities for the preparation of dyestufis by using difi'erent components; it, therefore, is not intended to limit the invention to the dyestuifs mentioned therein:

Diazotizing component Coupling component Tint 1. 1- amino 2 methyl 5- 2 (3 hydroxynaphthyl Reddishred 10. l-amino 2- chloreben- 2-(3-hydroxynaphthyl-2)- Reddishzene 4-hydroxy-bz-4"-bromoorange 6.7 benzo-pseudoaziminoben'zene ll. 1 amino 2 methyl-fld Brownishehlorobenzene red 12. 2 amino-1 (i-dibromodo Yellowishnaphthalene red 13. 4.4-diamino-3.3-dimedo Blackishthoxy-diphenyl violet l4. l-amino-Z-nitrobenzene do Yelldowishre 15. 1 -amino 2 methyl-4- 2-(3-hydroxy-7-methoxy- Brownishchlorobenzene naphthyl-2)-4-hydroxygarnet bz-4-methoxy-6.7 benzo pseudoaziminobenzene 16. l-amino -2.5-dichlorcdo Reddishbenzene brown 17. l-amino- 2-phenylsu1- do Do.

fonyl-benzene Y 18. l-amino-2-methyL5-nido Do.

trobenzene 19. l amino 4 benzoyl Currant amino 5-methoxy-2- chlorobenzene 20. 1 aminb-Z-methoxy-S- 2 (3 hydroxy 7-bromo- Bluish-red chlorobenzene naphthyl-2)-4-hydroxybz 4-bromo'6.7-benzo- The dyestufis may also be prepared on other fibers, as, for instance, on regenerated cellulose or on animal fibers.

Since an object of the present invention is to provide dyestuffs of good fastness properties, D which dyestufis are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims do not contain any substituents which are known to render organic compounds soluble in water or alkalies and to tend to depreciatethe fastness of the dyestuffs to alkalies. Substituents of this kind are, for instance, the sulfonic acid and the carboxylic acid group.

I'claim:

1. The water-insoluble azo-dyestuffs of the following general formula:

wherein R representsa radical of the benzene, naphthalene, diphenyl or anthraquinone series and Y stands for hydrogen, halogen or an alkoxy group, yielding, when produced on the fiber, dyeings the shades of which vary from orange to red to blue to black and being distinguished by good fastness properties. l

2. The water-insoluble azo-dyestuffs of the following general formula:

N Y 1L- N=NR wherein R represents a radical of the benzene, napthalene, diphenyl or anthraquinone series and Y stands for hydrogen, bromine or a methoxy group, yielding, when produced on the fiber, dyeings the shades of which vary from orange to red to blue to black and being distinguished by good fastness properties. f

3. The water-insoluble azo-dyestuffs of the fol- 1,315 lowing general formula:

N=N-R N N=N-R wherein R represents a radical of the benzene series and Y stands for hydrogen, bromine or a methoxy group, yielding, when produced on the fiber, dyeings the shades of which varyfrom orange to red to blue to black and being distinguished by good fastness properties.

'4. Fiber dyed with the azo-dyestufis as claimed in claim 1. ,1, 15C,

5. Fiber dyed with the aZo-dyestuffs as claimed in claim 2. r V

6. Fiber dyed with the azo-dyestuffs as claimed in claim 3. 7. The water-insoluble azo-dyestufi of the fol- Y lowing formula:

1? I 000m N p a i a yielding, when produced on the fiber, ayellowishred dyeing of good fastness properties.

8. Fiber dyed with the azo-dyestuff as claimed in claim 7. v

ARTHUR ZITSCHER. 

